EP2718274B1 - Procédés de séparation d'un oxyde d'alkylène par distillation extractive - Google Patents

Procédés de séparation d'un oxyde d'alkylène par distillation extractive Download PDF

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EP2718274B1
EP2718274B1 EP12728898.3A EP12728898A EP2718274B1 EP 2718274 B1 EP2718274 B1 EP 2718274B1 EP 12728898 A EP12728898 A EP 12728898A EP 2718274 B1 EP2718274 B1 EP 2718274B1
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solvent
stream
propylene oxide
acetaldehyde
column
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EP2718274A1 (fr
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Xiangmin Li
David W. Leyshon
Te Chang
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Lyondell Chemical Technology LP
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Lyondell Chemical Technology LP
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Definitions

  • the present invention relates to a process for the purification and recovery of propylene oxide which is formed from epoxidation of propylene with hydroperoxides derived from oxidation of isobutane, ethyl benzene or cumene.
  • the process improves the separation of light aldehydes, such as formaldehyde and acetaldehyde, from propylene oxide.
  • propylene oxide Approximately 14.5 billion pounds of propylene oxide are produced every year. Propylene oxide has many uses. Between 60 and 70% of all propylene oxide is converted to polyether polyols for the production of polyurethane plastics. About 20% of propylene oxide is hydrolyzed into propylene glycol, via a process which is accelerated either by thermal reaction or by acid or base catalysis. Other major products are polypropylene glycol, propylene glycols ethers, and propylene carbonate. To produce these end products, propylene oxide free of impurities is needed.
  • alkylene oxides including propylene oxide involve hydrochlorination and epoxidation of its corresponding olefins.
  • the oxidates used in the epoxidation processes are derived from tertiary or secondary hydrocarbons by direct oxidation with molecular oxygen; hence, they contain oxygenate impurites and precursors. Additional oxygenate impurites are also generated in the step of epoxidation of olefins.
  • Crude alkylene oxides, such as propylene oxide, particularly those produced from epoxidation with hydrocarbon oxidates contain a significant amount of oxygenated impurities difficult to separate from alkylene oxides.
  • the impurities generally include water, acids, alcohols, aldehydes, ketones and esters.
  • U.S. Pat. No. 3,338,800 teaches extractive distillation of alkylene oxides having from 3 to 18 carbon atoms with a paraffin or paraffin naphtha solvent. More particularly, this patent suggests that oxygenated impurities boiling within 5° C of the alkylene oxide may be separated by extractive distillation using acyclic paraffinic hydrocarbons as solvents having boiling points at least 35° C above the boiling points of the said impurities.
  • the problem addressed by this patent is that epoxide fractions produced by the direct oxidation of ethylenically unsaturated compounds with molecular oxygen in the liquid phase contain oxygenated impurities which, because their boiling points are similar to the desired epoxide product, cannot be separated by conventional distillation techniques.
  • U.S. Pat. No. 3,464,897 and 3,843,488 teach using hydrocarbon solvents of 8-20 carbon atoms can effective remove C5-C7 impurities from propylene oxide in extractive distillation.
  • U.S. Pat. No. 3,607,669 teaches a method for separating propylene oxide from water by distilling the mixture in the presence of acyclic or cyclic paraffin containing 8 to 12 carbon atoms by breaking water-propylene oxide azeotrope at elevated pressure.
  • U.S. Pat. No. 3,464,897 and 3,843,488 teach using hydrocarbon solvents of 8-20 carbon atoms can effective remove C5-C7 impurities from propylene oxide in extractive distillation.
  • U.S. Pat. No. 3,607,669 teaches a method for separating propylene oxide from water by distilling the mixture in the presence of acyclic or cyclic paraffin containing 8 to 12 carbon atoms by breaking water-propylene oxide aze
  • Patents such as 4,140,588 , 5,000,825 , 5,006,206 , 5,116,466 , 5,116,467 , 5,139,622 , 5,145,561 , 5,145,563 , 5,154,803 , 5,154,804 , 5,160,587 , 5,340,446 , 5,620,568 , 5,958,192 and 6,559,248 introduce various solvents in extractive distillation operations for propylene oxide purification.
  • U.S. Pat. No. 6,024,840 uses methanol as extractive solvent to remove acetaldehyde from propylene.
  • solvent methanol itself becomes close-boiling propylene oxide contaminant.
  • U.S. Pat. No. 7,705,167 teaches using water wash propylene oxide followed by contacting aqueous phase with hydrocarbon extractive solvent and subsequent distillation. These teachings are impractical for the existing plant improvement.
  • One embodiment relates to a systems, methods, and apparatuses for separating propylene oxide from a crude propylene oxide stream.
  • a crude propylene oxide stream for example an intermediate stream from a PO/TBA process, can be passed through an extractive solvent lights distillation column.
  • the crude propylene oxide stream comprises various impurities like formaldehyde, acetaldehyde, methyl formate, methanol, and water.
  • propylene oxide also known as epoxypropane, propylene epoxide, 1,2-propylene oxide, methyl oxirane, 1,2-epoxypropane, propene oxide, methyl ethylene oxide, methylethylene oxide
  • isobutane (IB) also known as 2-methylpropane
  • TBHP tert-butyl hydroperoxide
  • propylene also known as propene
  • TBHP tert-Butanol
  • 2-methyl-2-propanol 2-methyl-2-propanol
  • Acetaldehyde can also be formed in the PO/TBA process.
  • a possible mechanism for the formation of acetaldehyde is shown in Formula 7.
  • the concentrations of these impurities that end up in a crude PO stream from a PO/TBA process can vary.
  • Methyl formate can be present in an amount within a range having a lower limit and/or an upper limit, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the methyl formate lower limit and/or upper limit can be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79,
  • Methanol can be present in an amount within a range having a lower limit and/or an upper limit, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the methanol lower limit and/or upper limit can be selected from 0, 0.001, 0.002, 0.003, 0.0031, 0.0032, 0.0033, 0.0034, 0.0035, 0.0036, 0.0037, 0.0038, 0.0039, 0.0139, 0.0239, 0.0339, 0.0439, 0.0539, 0.0639, 0.0739, 0.0839, 0.0939, 0.1039, 0.1049, 0.1059, 0.1069, 0.1079, 0.1089, 0.1099, 0.1109, 0.1119, 0.1129, 0.1139, 0.1149, 0.1159, 0.116, 0.1161, 0.1162, 0.1163, 0.1164, 0.1165, 0.1166, 0.1167, 0.1168, 0.1169, 0.117, 0.1171, 0.1172, 0.1173, 0.1174, 0.1175, 0.1176, 0.1177, 0.2177, 0.3177, 0.4177, 0.5177, 0.6177, 0.7177, 0.8177, 0.9177, 1, 2, 3, 4, 5, and 10 weight percent
  • Acetaldehyde can be present in an amount within a range having a lower limit and/or an upper limit, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the acetaldehyde lower limit and/or upper limit can be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78,
  • Water can be present in an amount within a range having a lower limit and/or an upper limit, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the water lower limit and/or upper limit can be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8,
  • Formaldehyde can be present in an amount within a range having a lower limit and/or an upper limit, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the formaldehyde lower limit and/or upper limit can be selected from 0, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69,
  • Tables 1 and 2 show exemplary concentrations of key impurities in a crude PO stream from a PO/TBA process, each expressed as a weight percentage of the total composition of a crude PO stream from a PO/TBA process.
  • Table 1 Component Average weight percent MeF 0.06 Methanol 0.1172 Acetaldehyde 0.03 Water 0.16 Formaldehyde 0.005
  • Table 2 Component Average weight percent MeF 0.06 Methanol 0.0032 Acetaldehyde 0.03 Water 0.16 Formaldehyde 0.005
  • R1 and R2 can be hydrogen, or a C 1-10 alkyl.
  • Formation of an acetal can occur when the hydroxyl group of a hemiacetal becomes protonated and is lost as water, as illustrated in Formula 9, wherein R1, R2, and R3 can be hydrogen, or a C 1-10 alkyl.
  • a first embodiment of the present disclosure relates to a separation system 4 for removing impurities from a crude PO stream 10 from a PO/TBA process.
  • the crude PO stream 10 can include, but is not limited to, all of the impurities described above along with the desired product, propylene oxide.
  • the effluent stream 10 can be fed into a solvent-lights column 1. Most of the impurities in crude PO stream 10 can be removed in an overhead stream 11.
  • overhead stream 11 can be passed into a cooler 61, supplied with cooling fluid via cooling inlet line 64 and cooling outlet line 63.
  • the partially condensed outlet stream 65 from the cooler 61 flow into a reflux drum 62.
  • Vapor stream 12 from the reflux drum 62 can be fed to a vapor condenser 73, supplied with cooling glycol via inlet 76 and outlet 77.
  • the outlet 75 from condenser 73 can be fed into a separator 74 to produce a vapor purge stream 71 and a liquid purge stream 72.
  • a reflux stream 14 can be taken from wash inlet stream 13 and recycled to the solvent-lights column 1.
  • Wash inlet stream 13 can be fed into a water wash apparatus 2.
  • a water inlet stream 20 can also be fed into the water wash apparatus 2.
  • Solvents recovered from the water wash apparatus 2 can be recycled via recycle line 21 to the solvent-light column 1.
  • An aqueous purge stream 22 can also be removed from the water wash apparatus 2.
  • the bottom product 15 of solvent-lights column 1 can be passed through a reboiler 5.
  • a reboiler vapor stream 16 can be fed back to the solvent-lights column 1.
  • a reboiler bottoms product stream 17 can be added to solvent stripper column 3.
  • An overhead product stream 34 of the solvent stripper column 3 can include the desired propylene oxide product. Overhead product stream 34 can be processed to achieve further separation of propylene oxide.
  • a bottoms product stream 31 of the solvent stripper column 3 can be recycled to the water wash apparatus 2 via line 33 and/or to the solvent-light column 1 via line 32.
  • the solvent-lights column 1 can be made of any suitable material, including but not limited to carbon steel or stainless steel.
  • the solvent-light column 1 can include any suitable number of trays or theoretical trays, for example, about 25 theoretical stages. Feed stream 10 can be added at tray 11 to 15, counting from the bottom.
  • a suitable packing material can be employed in the solvent-lights column to enhance vapor-liquid contact. Suitable packing materials can be made from any material including glass, metal, plastic, and ceramic. The packing can be structured or dumped. Trays such as sieve trays, bubble cap trays or valve trays can also be used.
  • water wash apparatus 2 is very effective in removing key light impurities such as methyl formate, formaldehyde, acetaldehyde, and methanol. This helps keep hemiacetal or acetal formation as low as possible in the solvent-lights column 1. As already discussed, hemiacetal and acetal could enter into the solvent-light bottom product stream 15 and later breakdown in downstream columns as aldehydes to contaminate the propylene oxide product.
  • the reboiler temperature lower limit and/or upper limit can be selected from 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91' 92, 93, 94, 95, 96, 97, 98, 99, 100, 101' 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136,
  • unexpectedly beneficial results can be obtained by operating solvent-lights column 1 at a pressure within a range having a lower limit and/or an upper limit, each expressed in kPa (psig).
  • the solvent-lights column 1 can be operated at a pressure of 308.16 kPa (30 psig) or in a range of from 273.69 to 446.06 kPa 25 to 50 psig).
  • heavies such as hemiacetal or acetal formed in solvent-lights column 1
  • heavies can break down into aldehydes. These aldehydes can then be removed to the overhead of the solvent-lights column 1 and eventually be purged out via water wash apparatus 2 or via the vent purge 12 instead of staying in the column bottom and contaminating the PO product.
  • One embodiment of the present disclosure relates to a method for removing impurities from a crude PO stream from a PO/TBA process.
  • the crude PO stream can have a composition as previously defined.
  • the method can include passing the crude PO stream through a distillation column, such as solvent-lights column 1.
  • the distillation column can be operated at the temperatures and pressures as previously defined.
  • VLE Vapor Liquid Equilibrium
  • Table 3 presents the results of an experiment of binary acetaldehyde-propylene oxide VLE. Data was obtained for three pressures, 202.67, 302.65, 515.01 kPa (14.7 psia, 29.2 psia, and 60 psia).
  • This binary VLE data set shows a declining acetaldehyde to PO volatility at increasing pressure or temperature. Since the mixtures do not contain methanol, the effect on volatility could be only pressure or temperature although there is a possibility of acetaldehyde dimer or trimer formation. However, the acetaldehyde dimer or trimer formation equilibrium would be similar to hemiacetal/acetal equilibriums; they would be favored at low pressure/temperature.
  • Table 4 presents VLE data for PO-acetaldehyde-methanol system, for the effect of methanol on acetaldehyde volatility in propylene oxide.
  • the results demonstrate that at atmospheric pressure or low temperature, acetaldehyde volatility to PO declines with increasing methanol concentration in PO. As methanol concentration reaches about 2.5-3 wt%, acetaldehyde volatility to PO is approaching 1 which makes acetaldehyde inseparable from PO. When methanol concentration increases to about 4 wt%, acetaldehyde become heavier than PO with a relative volatility to PO near 0.82.
  • the water wash apparatus 2 will now be described in greater detail.
  • the overhead of Solvent Lights Column 1 (Stream 13) can be sent to water wash apparatus 2.
  • Water wash 2 can be carried out by mixing the solvent lights column 1 overhead with water and solvent.
  • Water supplied via wash inlet stream 20 can be used to remove the impurities from propylene oxide.
  • a solvent (Stream 33) can be used to minimize propylene oxide loss into the water phase. Adequate mixing is required to accomplish the best impurity removal. Adequate coalescing, and enough residence time in the decanter is also necessary to minimize entrainment of the aqueous phase in the organic effluent.
  • the organic effluent can be recycled back to the solvent lights column 1 via recycle line 21.
  • An aqueous purge stream 22 with a high concentration of impurities can be purged from the water wash apparatus 2.
  • the organic effluent, stream 21, can include an amount of the aqueous phase within a range having a lower limit and/or an upper limit, each expressed as weight percentages.
  • the range can include or exclude the lower limit and/or the upper limit.
  • the lower limit and/or upper limit for the amount of the aqueous phase in the organic effluent of the wash can be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, weight percent.
  • less than 0.1% of the aqueous phase can be present in the organic effluent of the wash or 10% of the aqueous phase can be present in the organic effluent of the wash.
  • the solvent stripper 3 can be made of any suitable material, including but not limited to stainless steel or carbon steel.
  • the solvent stripper 3 can include any suitable number of trays or theoretical trays, for example, about 10 trays.
  • Reboiler bottoms product stream 17 can be added at tray 1 - 10, preferably at tray 5.
  • a suitable packing material can be employed in the solvent-light column to enhance vapor-liquid contact.
  • Suitable packing materials can be made from any material including glass, metal, plastic, and ceramic. If packing is used, it can be structured or dumped. If trays are used, then can be sieve trays, bubble cap trays or valve trays.
  • the solvent stripper column 3 was made from 7.62 cm (3") Schedule 40 pipe. The entire height including the reboiler 83 was 223 cm (88 inch) tall.
  • the solvent stripper column 3 included a first packed section 81 and a section packed section 82, each packed section was 73 cm (28 3/4 inch) tall with 61 cm (24 inch) of packing.
  • the packing was made of 0.61 cm (0.24") Pro-pakTM packing, supported by conical screens resting on rings welded to the internal diameter of the column. Distribution rings were also used at the top of each packed section to ensure even distribution of liquid from above, over the packing.
  • the feed point 80 was in the middle of the vertical height of solvent stripper column 3, between the first packed section 81 and the section packed section 82.
  • a feed depicted as stream 17 in Figure 1 , was added to the solvent stripper column 3 at the feed point 80.
  • the solvent stripper column 3 was operated at 27.5 - 34.5 kPa (4-5 psig)
  • the steam flow to the reboiler 83 at the base of the tower was controlled to hold the weight percentage of PO in the bottoms at 0.5 to 1.5 wt %.
  • Vapor was removed from the top of the column, and fed to a total condenser. The condensed liquid was split into two parts. One part was fed back to the top of the solvent stripper column 3 as reflux. The rest of the liquid distillate was taken as PO product shown as stream 34 on Figure 1 .
  • the following examples were carried out in a continuous pilot plant.
  • the overview of the pilot unit is shown in Figure 1 .
  • Additional details of a solvent lights tower 1, used in the examples are shown in Figure 2 .
  • Additional details of solvent stripper column 3 are shown in Figure 3 .
  • the solvent lights tower 1 employed in the examples had a 5.1 cm (2") inside diameter and contained a bed of Pro-pakTM stainless steel protruded packing that was 335 cm (11 feet) deep.
  • the Pro-pakTM stainless steel protruded packing was 0.61 cm (0.24”) size.
  • the solvent stripper 3 in Figure 1 is also shown in more detail on Figure 3 .
  • the solvent stripper was 7.6 cm (3") inside diameter and contained a bed of Pro-pakTM stainless steel protruded packing, 0.61 cm (0.24”) size, which was 122 cm (4 feet) deep.
  • Example 1 describes the test period when the pilot unit solvent lights tower 1 as shown in Figures 1 and 2 was operated first at 273.69 kPa (25 psig)
  • the feed stream 10 comprising crude propylene oxide (an intermediate stream from a PO/TBA process) was fed to a point on the solvent lights tower 1 at the middle of the column.
  • Table 5 shows the concentrations of key impurities in the feed stream, each expressed as a weight percentage of the total composition.
  • Table 5 Component Average weight percent MeF 0.06 Methanol 0.1172 Acetaldehyde 0.03 Water 0.16 Formaldehyde 0.005
  • a plurality of temperature probes TE2112, TE2111, TE2110, TE2108, TE2107, TE2105, TE2113, TE2109, and TE2138 were employed and were positioned as shown in Figure 2 .
  • the temperature of the feed stream 10 was 27 degrees Celsius and the flow rate was 3.0 kg/hr.
  • Entering at the top of the tower was stream 32, comprising a lean solvent, pumped from the bottom of the solvent stripper 3, shown in Figure 1 .
  • the solvent stripper 3 is also shown in greater detail in Figure 3 .
  • the flow rate of lean solvent in stream 32 was 21.5 kg/hr.
  • the distillate, stream 11, from the solvent lights tower 1 was pumped back into the tower as reflux, stream 14, at a rate of 1.5 kg/hr.
  • the rest of the distillate, stream 13, was pumped into the water wash apparatus 2 at a rate of 185 gm/hr.
  • Two other streams were fed to the water wash apparatus 2: deionized water at a rate of 100 gm/hr and lean solvent from the bottom of the solvent stripper at a rate of 2.4 kg/hr.
  • the water wash apparatus 2 consisted of three parts: a mixer, a coalescer and a decanter.
  • the mixer was a 10.2 cm (4 inch) section of 1/16" OD tubing having an inside diameter of 0.030".
  • Downstream of the mixer was a coalescer (not illustrated) which was a 30.5 cm (1 foot) long bed of glass wool in a 0.951 cm (3/8") OD tube.
  • the decanter Downstream of the coalescer was a decanter (not illustrated) where the organic and aqueous phases were separated.
  • the decanter was a vertical glass pipe, 5.08 cm (2.0") ID by 30.5 cm (12") tall.
  • the washed organic phase overflowed from the top of the decanter and was sent to the top of the solvent lights tower 1.
  • the aqueous bottom layer from the decanter rich in methanol, methyl formate, acetaldehyde,and formaldehyde, was sampled and collected.
  • the organic and aqueous products from the decanter were used to calculate partition coefficients for the key impurities, as shown in Table 6.
  • Partition Coefficient Weight fraction in Aqueous phase Weight fraction in Organic phase Table 6 Component average Partition Coefficient Methyl Formate 1.6 Methanol 57 Acetaldehyde 6.6 PO 0.8 Formaldehyde 190
  • Table 6 shows that methanol, acetaldehyde and formaldehyde are easily extracted by the water wash block, since the partition coefficients are high.
  • Table 7 provides exemplary temperature, pressure and flow rate data for the pilot unit operation.
  • Table 7 Stream Temperature Pressure Flow Rate 10 69-84 °C 273.69-308.16 kPa 2.7- 3.3 kg/hr 11 77-84 °C 273.69-308.16 kPa 1.65- 1.72 kg/hr 12 63-72 °C 273.69-308.16 kPa 2- 13 gm/hr 13 50-68 °C 273.69-308.16 kPa 160 - 200 gm/hr 14 50-68 °C 273.69-308.16 kPa 1.49 - 1.5 kg/hr 15 106- 119 °C 273.69-308.16 kPa 24-28 kg/hr 16 106- 119 °C 273.69-308.16 kPa 17 16-20 °C 273.69-308.16 kPa 24-28 kg/hr 20 20-26 °C 273.69-308.16 kPa 100-101 gm/h
  • the vapors from the solvent lights tower 1, which did not condense in cooler 61 shown in Figure 2 were collected and analyzed.
  • the bottoms 17 from the solvent lights tower 1 were sent to the middle of the solvent stripper tower 3, as shown Figure 1 .
  • the solvent stripper tower 3 was operated at 138.9 kPa (4 psig).
  • the purpose of the solvent stripper tower 3 was to recover the propylene oxide product as a distillate (overhead) stream 34 and the lean solvent as the bottoms stream 31.
  • the feed rate to the solvent stripper tower 3 was 26.9 kg/hr.
  • the reflux rate to the solvent stripper tower 3 was 8.0 kg/hr.
  • the bottoms product 31 from the solvent stripper tower 3 was split into two streams (stream 32 and stream 33), one feeding the top of the solvent lights tower and the other feeding the wash block mixer, shown as unit 2 on Figure 1 .
  • the operating temperatures at the solvent-light column 1 also increased by about 5 degrees Celsius. At higher column temperature, a large amount of hemiacetals and/or acetals are converted to the form of aldehyde plus alcohol. Aldehyde and alcohol are then distilled overhead in the solvent lights tower and removed by both water wash and vapor purge.
  • Formaldehyde is primarily removed into aqueous purge. Acetaldehyde is removed into both purges. As shown in Table 6 water wash operation, formaldehyde is favorably partitioning into the aqueous phase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Claims (8)

  1. Procédé de séparation d'oxyde de propylène d'un courant d'oxyde de propylène brut, le procédé comprenant le passage du courant d'oxyde de propylène brut à travers une colonne de distillation extractive, dans lequel la colonne de distillation est mise en oeuvre à une pression dans une plage supérieure à 273,69 à 446,06 kPa (25 à 50 psi manométriques) et dans lequel la colonne de distillation extractive utilise une paraffine en C8 à C20 en tant que solvant d'extraction.
  2. Procédé selon la revendication 1, dans lequel la tête de colonne de distillation inclut un tambour de lavage à l'eau.
  3. Procédé selon la revendication 2, dans lequel une partie du distillat de tête est mélangée à un solvant d'eau et de paraffine dans un mélangeur statique pour former un mélange, et dans lequel le mélange est alimenté au tambour de lavage à l'eau.
  4. Procédé selon la revendication 3, dans lequel le tambour de lavage à l'eau permet à des gouttelettes du mélange de coalescer et de se séparer en une phase organique supérieure et une phase aqueuse inférieure, dans lequel la phase organique supérieure est alimentée à la tête de colonne de distillation extractive dans le cadre d'un reflux, et dans lequel la phase aqueuse inférieure est éliminée pour un traitement ultérieur.
  5. Procédé selon la revendication 1, dans lequel le courant d'oxyde de propylène brut comprend de 0,001 à 0,5 % en poids de méthanol, sur la base de la composition totale du courant d'oxyde de propylène brut.
  6. Procédé selon la revendication 1, où le procédé produit un courant comprenant moins de 50 ppm de formaldéhyde.
  7. Procédé selon la revendication 1, où le procédé produit un courant comprenant moins de 30 ppm d'acétaldéhyde.
  8. Procédé selon la revendication 1, dans lequel la colonne de distillation extractive comprenant le rebouilleur est mise en oeuvre à une température dans une plage allant de 70 à 150 degrés Celsius.
EP12728898.3A 2011-06-07 2012-06-07 Procédés de séparation d'un oxyde d'alkylène par distillation extractive Active EP2718274B1 (fr)

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US13/155,136 US8981133B2 (en) 2011-06-07 2011-06-07 Alkylene oxide separation systems, methods, and apparatuses
PCT/US2012/041349 WO2012170685A1 (fr) 2011-06-07 2012-06-07 Procédés de séparation d'un oxyde d'alkylène par distillation extractive

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CN109851590A (zh) * 2017-11-30 2019-06-07 中国石油化工股份有限公司 环氧丙烷的纯化方法
CN110003136B (zh) * 2019-04-26 2023-08-01 江苏扬农化工集团有限公司 一种使用高效助剂脱除hppo工艺中醛酮杂质的方法和装置
CN112694455B (zh) * 2019-10-23 2023-08-08 中国石油化工股份有限公司 加氢脱除醛和酮的系统及方法

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CN103562192B (zh) 2016-08-17
KR101627439B1 (ko) 2016-06-03
US20120312680A1 (en) 2012-12-13
WO2012170685A1 (fr) 2012-12-13
CN103562192A (zh) 2014-02-05
EP2718274A1 (fr) 2014-04-16
JP6105568B2 (ja) 2017-03-29
BR112013031148A2 (pt) 2016-08-16
US8981133B2 (en) 2015-03-17
ES2658153T3 (es) 2018-03-08
KR20140044847A (ko) 2014-04-15

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